Phenoxybenzonitriles

ABSTRACT

Phenoxybenzonitriles, halo-substituted on the phenoxy ring and halo- or alkyl-substituted on the benzonitrile ring ortho to the para-cyano position, form a new class of herbicides. These substituted phenoxybenzonitriles and herbicidal compositions containing them are highly effective as pre-emergence and postemergence herbicides, especially at low use concentrations. They are highly effective against Crabgrass, Yellow Foxtail grass and Barnyard grass, annual grass weeds which reproduce by seed. They are also highly effective against Johnson grass, a perennial grass weed which reproduces by seed and underground rhizomes, and Pigweed, an annular broadleaf weed which reproduces by seed.

United States Patent [191 Theissen Dec. 2, 1975 I 1 PHENOXYBENZONITRILES Robert James Theissen, Union County. NJ.

22 Filed: Feb. 23, 1973 211 Appl. No.: 335,408

Related US. Application Data [63] Continuation-impart of Ser. No. 69,959, Sept. 4,

i970. abandoned.

[75] Inventor:

[52] US. Cl. 260/465 F; 71/105 [51] Int. Cl. C07C 121/75 [58] Field of Search 260/465 F; 7l/l05 [56] References Cited UNITED STATES PATENTS 3.535.365 10/1970 Weinstock et al. 260/465 FOREIGN PATENTS OR APPLICATIONS 1,912,600 9/1969 Germany 951.651 3/1964 United Kingdom Primary Examiner-Lewis Gotts Assistant Examiner-Dolph H. Torrence Attorney. Agent, or Firm-Charles C. Haggett;

Hastings S. Trigg [57] ABSTRACT Phenoxybenzonitriles, halo-substituted on the phenoxy ring and haloor alkyl-substituted on the benzonitrile ring ortho to the para-cyano position. form a new class of herbicides. These substituted phenoxybenzonitriles and herbicidal compositions containing them are highly effective as pre-emergence and post-emergence herbicides, especially at low use concentrations. They are highly effective against Crabgrass, Yellow Foxtail grass and Barnyard grass, annual grass weeds which reproduce by seed. They are also highly effective against Johnson grass, a perennial grass weed which reproduces by seed and underground rhizomes. and Pigweed, an annular broadleaf weed which reproduces by seed.

5 Claims. No Drawings 1 2 i an integer from 1 to 5; their use as herbicides; and her- PHENOXYBENZONlTRlLES bicidally eflective compositions containing at least one (.ROSSREFERENCE To REL/KPH) ot' the above CUI'HPOUHLlStlIIKl va carrier thlerel'or. I An important part ol this invention is that X and/or APPLlCAllONS q y I may be alkyl. Compounds according to the invention This application is a continuation-in-part olcopendwhich are alkyl-substituted are somewhat more herbiing Ser. No. 69.95), tiled Sept. 4. W70. entitled cidally effective than their halogen counterparts. Ap- S'll'l'U'l'l-ll) PHENOXYBENZONITRILES AS HER- plicant has no knowledge of such alkyl-substituted BlClDF-S 11ml ilhllmlmwdcompounds in the prior herbicide art. Accordingly BA(.K(I;R()UND OF THE INVENTION those compounds in which and/or Y are alkyl are preferred embodiments 01 this invention.

1. Field ol the Invention This invention is directed to new compounds of sub- DESCRIP'IION OF SPECIFK EMBODlMhN l S Smutcd PhcnlxyhcnzPllltrllcs 11ml lhclr P and As will be noted from the formula. the compounds of P g F hcvrhlcldci the present invention are phenoxybenzonitriles. halo- Dcscnlnmn the substituted on the phenosy ring and haloor alkyl-suh- In US. Pat. N 3.3 15 35 thcrc l5 (llscklscd stituted on the benzonitrile ring ortho to the para- P thc Structure cyano position. Mono-substituted compounds, i.e..

. m compounds which are monohaloor monoalkyl-sub- 2 stituted on the benzonitrile ring are highly advantageous. Examples of these compounds are Z-chloro-4- 3 0 CN (2,4'-dichlorophenoxy)benzonitrile and 2-inethyl-4- (2',4'-dichlorophenoxy)benzonitrile. The methyl-subas a herbicide. France Pat. No. 1.502.538 discloses a ifi igl lg gr lggg {Dr wmlmund thc Stmcturc Non-limiting examples of the compounds embodied lor use in this invention include: O N 2'methyl-4-( 2 ',4-dichlorophenoxy )benzonitrilc. O2N O Z@ CN 2-ethyl-4(2.4-dichlorophenoxy)bcnzonitrile. 2-propyl-4-( 2 ,4'-dich lorophenoxy )benzonitrile.

2-amyl-4-(2'.4-dichlorophenoxy)benzonitrile.

as a herbicide. Britain Pat. No. 951.651 discloses com- F i sy; fs gf v aw a pounds of the structure j f mm) f".

-isopropyl-4-( 2 ,4 -dichlorophenoxy )benzonitrile. Z-sec-butyl-4-( 2 ,4'-dichlorophenoxy )bcnlonitrile. Cl CN C1 2-allyl-4-( 2 .4'-dichlorophenoxy )benzonitrile.

@- O n Z-cyclopropylmethyl-4-(2'.,4'-dichlorophenoxy)bcnzonitrile,

4n 3-chloro-4-( 2 ',4-dichlorophenoxy )benzonitrile. wherein il' II is l. the chlorine is ortho or para. and il ll gb'dlchlum'dd 2[*4Idlfhloriiplwnoxy)he'mmitme is 2. the chlorines are ortho and para. as herbicides. Q 2 'dlchlomphenoxy)hen' (ierinanv Pat. No. [.9 I 2.600 discloses compounds of hmnnkh thc swucnlrc Z-lluoro-4-( 2.4-dichlorophenoxy )benzonitrile.

Z-chloro-4-( Z ,4',o'-trichlorophenoxy )benlonitrile.

Z-methyl-4-( 2'-chloro-4-lluorophenoxy )benzoni- Zchloro-4-(2'.-l-dilluorophenoxy)benzonitrile and Xn the like.

So The compounds ol the present invention are highly wherein X may be an alkyl group or halogen, as herbicflbctlw hcrhlcldcs g 115 cities centrations as compared to similar compounds which are unsubstituted on the benzonitrile ring or if substi- SUMMARY [HE lNVEN HON tutcd thereon are not substituted ortho to the para- This invention provides compounds having the strucw lmsitltmtural l'ormula: It is not known why ortho substitution with respect to a para positioned cyano group on the benzonitrile ring X improves the effectiveness of these compounds. nonetheless their overall greater herbicidal activity is readily 0 CN 00 apparent in herbicidal screening tests. The compounds olthis invention also retain substantially their high ac- Zn Y tivity as herbicides at relatively low use concentrations.

e.g.. from about I to about 5 pounds per acre. wherein X is hydrogen. halogen or lower alkyl. straight The compounds of this invention are readily preand branched chain alkyl. alkcnyl. and cycloalkyl (e.g.. Y is halogen (e.g.. fluorine. chlorine. bromine and iodine) or lower alkyl (cg. -C Z is halogen (c.g.. lluorine. chlorine. bromine and iodine). and ii is pared by the reaction of a suitable halogenated benzonitrile (e.g.. 4-chloro-Z-methylbenzonitrile) with a metal salt of 2.4-dichlorophenol in a suitable solvent. as in the following examples.

EXAMPLE 1 2-methyl-4-( 2 ',4-dichlorophenoxy )benzonitrile A stirred solution of 4-chloro-2-methylbenzonitrile (7.85g.. 0.05 mole) and the potassium salt of 2.4- dichlorophenol (10.07g., 0.05 mole) in 50 ml. of dimethyl acetamide was heated for 30 hours at 150C. The cooled reaction mixture was diluted with 200 ml. of water to precipitate a brown oil. From this oil, an ether extract yielded 12.0g. of an oil. A vacuum distillation of the oil gave 8.6g. of 2-methyl-4-( 2,4'-dichlorophenoxy)benzonitrile with a boiling point of l63l66C at 0.05 mm Hg. and a melting point of 5255C.

EXAMPLE 2 2-methyl-4-( 2 -chloro-4-fluorophenoxy )benzonitrile A stirred solution of 4 chloro-2-methylbenzonitrile (4.7g. 0.03 mole) and the potassium salt of 2-chloro-4- tluorophenol (554g. 0.03 mole) in 40 ml of dimethyl acetamide was heated for 48 hours at 150C. The cooled reaction mixture was diluted with 200 ml. of water to precipitate a brown oil. An ether extract yielded 7.6g of 2-methyl-4-( 2 ehloro-4'-fluorophenox y)benzonitrile as a brown oil in about 90% purity.

EXAMPLE 3 2-chloro-4-( 2 ',4-dichlorophenoxy )benzonitrile A stirred solution of 2,4-dichlorobenzonitrile (5l.6g.. 0.03 mole) and the potassium salt of 2,4- dichlorophenol (603g, 0.03 mole) in 250 ml. of dimethyl acetamide was heated for 24 hours at 120C. The cooled reaction mixture was diluted with 1000 ml. of water and the resultant oil was extracted with ether. Evaporation of the ether solution gave 88.0g. of brown oil. Analysis by v.p.c. showed a 2:1 mixture of the desired compound and the isomeric 4-chloro-2-(2,4- dichlorophenoxy) benzonitrile. A series of fractional crystallizations from 60-1 C petroleum ether gave the desired 2-chloro-4-(2',4'-dichlorophenoxy)benzonitrile with a melting point of 6974C. The minor isomeric by-product melted at 1 101 13C.

EXAMPLE 4 2-chloro-4-(2,4,6-trichlorophenoxy')benzonitrile A "tirred solution of 2,4-dichlorobenzonitrile (5. 1 6g., 0.03 mole) and the potassium salt of 2,4,6-trichlorophenol (7.06g., 0.03 mole) in ml of dimethyl acetamide was heated for about 60 hours at 150C The cooled reaction mixture was diluted with 200 m1 of water to precipitate a brown oil which was extracted with ether. The initial brown oil amounting to 8.4g. was dissolved in hot heptane. Upon cooling, a yellow solid was obtained. It was collected by filtration and dried to give 3.9g. of 2-chloro-4-(2,4,6-trichlorophenoxy)- benzonitrile with a melting point of 1081 16C.

In illustration of this invention, the embodiments 2- methyl-4-( 2 ,4-dichlorophenoxy )benzonitrile. 2- methyl-4-( 2 -chloro4'-fluorophenoxy )benzonitrile, 2-chloro-4-( 2 ,4'-dichlorophenoxy )benzonitrile and 2-chloro-4-( 2,4, 6-trichlorophenoxy)benzonitrile were subjected to tests for herbicidal activity as described hereinafter with the test results being set forth in the Tables following the test descriptions. For comparison purposes, the Tables include results obtained with similar compounds, i.e., 4-(2,4-dichlorophenoxy)benzonitrile which is unsubstituted 0n the cyanobearing ring, 6-chlo'ro-2-(2',4-dichlorophenoxy) benzonitrile which has an ortho-cyano group, and 6-methyl-2-(2,4-dichlorophenoxy)benzonitrile* which also has an orthocyano group. All three of these compounds, labelled. respectively Examples 5-7, illustrate the improved retention of activity of the compounds embodied herein at lower use concentrations.

* specially synthesized by applicant in a manner similar to that of Examples l and 2.

HERBlClDE TESTING METHOD The test species propagated for testing are:

Crahgrass Pigwecd Yellow Foxtail grass Turnip Johnson grass Cotton Barnyard grass Corn Bean Each specie is planted individually in 3 inch plastic pots containing potting soil. Four seeds each of the corn, bean, and cotton are seeded to a depth equal to the diameter of the seed. The other species are surface seeded and sprinkled with screened soil in an amount sufficient to cover the seed. Immediately after planting,

all pots are watered by sub-irrigation in greenhouse trays. Pots for the pre-emergence phase of testing are seeded one day before treatment.

Planting dates for the post-emergence phase of testing are varied so that all seedlings will reach the desired stage of development simultaneously. The proper stage of development for treatment in the post-emergence tests is as follows:

(irasses: 2 inches in height Pigweed 8: Turnip: l or 2 true leaves visible above cotyledons point at primary leaf node.

Spray applications are made in a hood containing a movable belt and fixed spray nozzle. For passage through the spray hood, one pot of each species (P emergence phase) is placed on the forward half of a wooden flat and one pot of established plants (P emergence phase) is placed on the rear half of the flat. Treatments are moved to the greenhouse after spraying. Watering during the observation period is applied only by sub-irrigation.

Compounds are screened at rates of application equivalent to 8, 4 and 2 pounds actual/acre in a spray volume of 38 gal/acre. Spray hood constants required to deliver the above volume are as follows:

Belt Speed: 2 mph Air Pressure: adjusted to provide 38 gpa delivery Nozzle Tip: 8003E (provided uniform cross-section flat spray) t 8 Pounds per Acre Rate 1. 1 24 grams compound 2. 49 ml. acetone as solvent 3. 1 ml. xylene-Atlox 3414 (surface-active emulsifier) 4 Pounds per Acre Rate Johnson grass, a perennial grass weed which reproduces by seed and underground rhizomes and is primarily a problem in field crops. Also. they prove to be effective against Pigweed, an annual broadleaf weed *Herbicidal activity is measured in pe rccnt effectiveness 1. 0.62 grams compound 5 which reproduces by seed and is one of the most seri- 2. 49 ml. acetone as solvent ous broadleaf weed problems in major agronomic 3. 1 ml. xylene-Atlox 3414 crops.

7 P d A R t The compounds of this invention exhibit considerl S per ere a e able preand post-emergence herbicidal activity and l. 0.31 grams compound 10 are disclosed for use in various ways to achieve pre- 2. 49 ml. acetone as solvent emergence or post-emergence contact control of unde- 3. 1 ml. xylene-Atlox 3414 sirable herbs. They can be applied as the toxic compo- Compounds that are insoluble in the customary solnents in herbicidal compositions of the compound and vents are formulated either in the Waring Blender and toxic components in herbicidal compositions of the applied as suspensions with suitable carriers, or dispercompound and a carrier. The compositions can be up sants or prepared initially as wettable powders. Complied as dusts, as liquid sprays, or as gas-propelled pounds that are not available in sufficient quantity for sprays and can contain, in addition to a carrier, addimachine spraying are applied by hand with a De Vilbiss tives such as emulsifying agents, wetting agents, bindatomizer. ing agents, gases compressed to the liquid state. odor- Two weeks after treatment, a preand post-emer- 30 ants, stabilizers. and the like. A wide variety of liquid gence injury or control is visually rated as percent inand solid carriers can be used in the herbicidal compojury or control (percent effectiveness). sitions. Non-limiting examples of liquid carriers include TABLE 1 HERBlClDAL ACTlVlTY* OF THE PHENOXYBENZONlTRlLES OF THIS INVENTION Example Concentration Yellow Foxtail Johnson Barnyard Compound lbs/acre C rabgrass grass grass grass Pigwccd Turnip Cotton Corn Bean Pro-Emergence Activity I 1 s 100 100 100 o 30 so 4 so 100 90 70 100 0 so o 1()() 2 90 so 9o 40 loo 2o 0 2o so 2 9o 9o o 4 so 90 so 2o 3o 0 3 s 100 2o o 4 4 so so 20 50 5o 2 70 so 5o 30 loo 0 so so 100 4 s so 90 I so 70 30 o 100 2 4o 30 2o o 2o o 5 s 100 100 so 100 o 30 o loo ,4 4o 20 20 so 2o 30 0 so 6 s 0 o 0 7o o 1()() 0 too 7 4 so so 70 o so so 0 loo Herbicidal activity is measured in percent elllectiveness "Formulations prepared according to method disclosed on page 9 1.55 grams of compound used TABLE 2 HERBlClDAL ACTlVlTY* OF THE PHENOXYBENZONITRILES OF THIS INVENTION Example Concentration Yellow Foxtail Johnson Barnyard Compound lbs/acrc C rabgrass grass grass grass Pigweed Turnip Cotton C orn Bean Post-Emergence Activity 1 8 100 so so too 30 so too 4 so 40 too so loo 2 I0 40 so 20 4o 4 40 o 20 2o 3 s so 30 so 50 7o 4 s so 9o 40 7o 30 so 2 so 9o 40 so 7o so so 5 s 90 90 so so so so :o 100 4 so 4o 30 so so 5o 40 100 s s so 50 2o 50 40 o 0 so 7 s 40 40 3o 4o o 2o 30 Formulations prepared according to method disclosed on page 9 1.55 grams of compound used From the data in this Table, it will be noted that the substituted phenoxybenzonitriles of this invention have a broad range of both preand post-emergence herbicidal activity. The specific embodiments of these compounds used for testing, those of examples 1, 2, 3 and 4 show high effectiveness against Crabgrass, Yellow Foxtail grass and Barnyard grass, annual grass weeds which reproduce by seed and are problems in lawns and field crops. They also prove highly effective against water, organic oils such as kerosene, light oils and medium oils, and vegetable oils such as cottonseed oil. Non-limiting examples of solid carriers include talc, bentonite, diatomaceous earth, pyrophyllite, fullers earth, gypsum, flours derived from cotton seeds, and nut shells and various natural and synthetic clays having a pH not exceeding about 9.5.

The amount of the compounds of this invention utilized in herbicidal compositions will vary rather widely.

It depends to some extent upon the type of composition in which the material is being used. the nature of the condition to be controlled. and the method ofapplication (i.e.. spraying. dusting. etc. In the ultimate herbicidal compositions, as applied in the field. herbicide concentrations as low as 0.000! weight percent of the total composition can be used. in general. compositions. as applied. containing about 0.05 weight percent herbicide in either liquid or solid carrier give excellent results. In some cases. however. stronger dosages up to about 10 weight per cent may be required.

in practice. herbicidal compositions are usually prepared in the form of concentrates. which are diluted in the field to the concentration desired for application. For example. the concentrate can be a wettable powder containing large amounts of a compound of this invention. a carrier (e.g.. attapulgite or other clay) and wetting and dispersing agents. Such a powder can be diluted prior to application. by dispersing it in water to obtain a sprayable suspension containing the concentration of herbicide desired for application. Other concentrates can be solutions that can be later diluted. e.g..

with kerosine. Thus. it is within the contemplation olthis invention to provide herbicidal compositions containing up to about 80 per cent. by weight of the composition. of a herbicidal compound of this invention. Accordingly. depending upon whether it is ready for application or it is in concentrated form. the contemplated herbicidal compositions contain between about ().()()()I per cent and about 80 per cent. by weight ofthe composition. of a herbicidal compound of this invention. and a carrier. liquid or solid. as defined hereinabove.

Although the present invention has been described with preferred embodiments. it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of this invention. as those skilled in the art will readily understand.

What is claimed is:

l. A compound having the formula:

wherein X is hydrogen. Y is halogen or lower alkyl. Z is halogen and n is an integer of from I to 3.

2. The compound of claim I having the formula:

Cl CH 3. The Compound of claim 1 having the formula:

C1 CH 4. The compound of claim I having the formula:

5. The compound of claim 1 having the formula: 

1. A COMPOUND HAVING THE FORMULA:
 2. The compound of claim 1 having the formula:
 3. The compound of claim 1 having the formula:
 4. The compound of claim 1 having the formula:
 5. The compound of claim 1 having the formula: 